TW200806467A - Flexible laminate having thermoplastic polyimide layer and method for manufacturing the same - Google Patents

Abstract

Disclosed is a flexible laminate comprising a metal foil layer/a thermoplastic layer or/and a conductive circuit layer/a thermoplastic polyimide layer, which is obtained by bonding a metal foil layer or a conductive circuit layer to at least one side of a thermoplastic polyimide layer. In this flexible laminate, the thermoplastic polyimide layer is made of a thermoplastic polyimide resin film or sheet which is obtained by melt-extruding a thermoplastic polyimide resin. Alternatively, the thermoplastic polyimide layer is made of a biaxially stretched thermoplastic polyimide resin film or sheet. Such a flexible laminate can be easily produced by a lamination method wherein a thermoplastic polyimide resin film (1) and a metal foil (2) or a conductive circuit layer (4) are bonded by heat and pressure, and has excellent heat resistance, electrical characteristics and mechanical strength inherent in polyimides. When a biaxially stretched thermoplastic polyimide resin film or sheet is used, the flexible laminate can be improved in dimensional stability and solder heat resistance.

Description

200806467 (1) Description of the Invention [Technical Field] The present invention relates to a flexible laminate having a thermoplastic polyimide layer as an adhesive layer and a method for producing the same. [Prior Art] With the increase in the density of electronic devices in recent years, the printing back Φ boards used in the development of multilayers have been multi-layered, and flexible circuit boards have mostly used multilayer structures. The polyimine resin film is excellent in flexibility and flexibility, and has excellent properties such as mechanical strength, heat resistance, and electrical properties. Therefore, an adhesive such as an epoxy resin and a copper foil have been used since the prior art. The three-layer substrate is widely used in the manufacture of recording automatic bonding (TAB) products which can be described as flexible circuit boards and flexible printed circuit boards. However, since the adhesive is used, the dielectric constant is changed. High and low heat resistance. Φ In addition, since the demand for miniaturization of electrical and electronic products has become high in recent years, flexible printed circuit boards used in devices with a narrow space have been required to be further thinned and miniaturized. From the viewpoint of improvement in circuit density and improvement in folding endurance, a two-layer substrate in which a copper layer is directly provided on the surface of a polyimide film is omitted. However, since the thermosetting polyimide film is not heated and melted, it cannot be directly bonded to the copper layer. Therefore, the prior art forms a copper layer on the surface of the polyimide film without using an adhesive. The method of forming a 2-layer base-5-200806467 (2) plate has been widely used for vapor deposition, casting, and plating. However, any of the methods has disadvantages in that a two-layer substrate of a copper layer is formed on the surface of the polyimide film by vapor deposition using a vapor deposition method, and the copper layer and the polyimide film are insufficient in adhesion. In addition, there is also the problem of reduced mobility resistance. On the other hand, the casting method, because it is necessary to coat the polyfluorene acid of the polyfluorene-imine precursor on the copper box, and to carry out the hydrazine imidization at a high temperature, the manufacturing steps are complicated and the productivity is poor, and When the impurities are mixed, the voids are liable to occur, or the substrate to be manufactured is liable to warp, which is difficult to be practical. Therefore, the most commonly used method is the plating method, the electroless plating method or the combination of the electroless plating method and the electroplating method is a general method, but the copper layer formed by electroless copper plating, There is also a lack of adhesion to the polyimide film, and the peel strength of the copper layer is low, which is a problem of reliability as a substrate. Further, the disadvantages common to the above respective methods include the disadvantage that only one side can be performed each time when the layer of the conductor layer is combined, and the step of performing double-sided lamination requires a complicated number of steps. In addition, the use of thermoplastic polyimides has also been proposed in many patent documents (refer to Patent Documents 1 to 8), but the prior art polyimine is thermoplastic, because it is not suitable for melt forming, In the method proposed in the above patent document, a polyglycine of a precursor is cast and applied onto a base film, and after heating, a film is obtained by a hydrazine imidization reaction (dehydration condensation reaction), and an epoxy resin is used. Such as the laminating method of laminating the metal foil, etc., so the method is also the same as above because of the -6 - 200806467 (3)

In the case of the use of the adhesive, the dielectric constant is increased, and the heat resistance is lowered. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei 8-244168 (Patent Document 2) JP-A-2002- 1 0 2 2 2 7 [Patent Document 3] JP-A-2002-192 7-89 (PATENT DOCUMENT 5) OPERATION 2 0 0 3 - 2 5 1 7 7 Japanese Laid-Open Patent Publication No. 2005-19265 (Patent Document No. JP-A-2005-193541) [Problems to be Solved by the Invention] The present invention has been made to solve the above-described problems of the prior art, and its main object is to provide a heat-resistant property which is excellent in polyetherimide by simply being produced by a lamination method. Flexible laminate of metal foil layer/thermoplastic polyimide layer or/and conductor loop layer/thermoplastic polyimide layer of electrical properties, mechanical strength. Further, an object of the present invention is to provide a film which can be easily produced by a lamination method, and which has excellent heat resistance, electrical properties, mechanical strength, and excellent dimensional stability and solder heat resistance. A flexible laminate of a metal foil layer/thermoplastic polyimide layer or/and a conductor loop layer/thermoplastic polyimide layer of such characteristics. The object of the present invention is to provide a layer of a polyimide layer and a conductor layer (metal foil) by heat-pressurizing a thermoplastic polyimide film without using a layer of viscous 200806467 (4) The method of producing the above flexible laminate by the press method with excellent productivity and low cost. Further, an object of the present invention is to provide a flexible laminate which is excellent in productivity, low-cost, and excellent in properties such as dimensional stability and solder heat resistance by a lamination method without using an adhesive. [Means for Solving the Problem] φ In order to achieve the above object, according to the present invention, there is provided a metal foil layer/thermoplastic polymer formed by adhering a metal foil layer or a conductor loop layer on at least one side of a thermoplastic polyimide layer. a flexible laminate of a quinone imine layer or/and a conductor loop layer/thermoplastic polyimide layer; characterized by the above thermoplastic polyimide layer being obtained by melt-extruding a thermoplastic polyimide film resin a thermoplastic polyimide film or sheet (hereinafter collectively referred to as "thermoplastic polyimide film"), or a biaxially stretched thermoplastic polyimide film or sheet (hereinafter collectively referred to as "biaxially stretched thermoplastic polymer" Flexible laminate made of imine Φ resin film"). In a preferred embodiment, the thermoplastic polyimide resin preferably has a glass transition temperature (Tg) of 180 to 2 80 ° C or a extrusion temperature of 30 ° C higher than the melting point of the resin. The shear viscosity measured in the range of SOOtsecT1] is preferably 5X101~lx104 [Pa·S]. Here, the melt viscosity [Pa · S] of the thermoplastic polyimide resin is measured by the Shimadzu FLO W TESTER CFT-5 00 according to JIS K-7199, but is not limited thereto, and may be The enthalpy measured under the same conditions. The above-mentioned biaxially stretched thermoplastic polyimide film can be a thermoplastic polyimide film obtained by a casting method as in the prior art of -8-200806467 (5), by means of a biaxial stretching In a preferred embodiment, the thermoplastic polyimide film obtained by melt-extruding the thermoplastic polyimide, as described above, and the biaxially stretched thermoplastic poly-imide obtained by biaxial stretching The resin film is preferably a thin v film of the above biaxially stretched thermoplastic polyimide film, and the thermal expansion α 2〇-2〇〇 of either the MD direction (longitudinal direction of the film) and the TD direction (film width direction) In the range of φ of 5 parent 10_6 to 30 parent 1〇-6/:^, the difference between the thermal expansion ratio α2〇-2()() in the MD direction (longitudinal direction of the film) and the TD direction (film width direction) It is preferably 2〇χ1 ((6/Κ6 or less); and more preferably, the above-mentioned biaxially stretched thermoplastic polyimide film is desired to have a glass transition temperature Tg of glass transition temperature Tg of the thermoplastic polyimide film before stretching. 10~80°C higher. Again, the so-called in this manual The glass transition temperature Tg is the glass transition temperature measured by thermomechanical analysis (TMA) according to the method described in "5.17.1 TMA method" of JIS C 6481: 1996. • In other preferred embodiments, the above thermoplastic polyfluorene The imine resin is a knot-crystalline thermoplastic polyimide resin or a mixture of a crystalline thermoplastic polyimide, a resin, and another thermoplastic resin having a melting point of 280 to 350 ° C. In a preferred embodiment, the thermoplastic polyimide resin is a thermoplastic polyimine resin having a repeating structural unit of the general formula (1) to be described later, preferably a repeating structural unit having the formula (5) described later. The thermoplastic polyimine resin is a ratio of the molar number m of the structural unit of the formula (6) to the molar number of the structural unit of the formula (7), m/n is 4 to 9 s, which will be described later. Heat of the repeating structural unit of the formula (6) and the formula (7) - 200806467 (6) Plastic polyimine resin. Further, in other preferred embodiments, the formula (6) and the formula (8) are described later. The repeating structural unit of the thermoplastic polyimine tree, and the following formula (6) The thermoplastic structure of the repeating structural unit represented by the formula (8) and the repeating structural unit represented by the formula (8) is 1:0 to 0.75: 0.25. A method for producing a laminate, the basic form of which comprises a metal foil layer/thermoplastic polyimide layer formed by adhering a φ metal foil layer or a conductor loop layer on at least one surface of a thermoplastic polyimide layer. A method for producing a flexible laminate of a conductor loop layer/thermoplastic polyimide layer; characterized by a thermoplastic polyimide film obtained by melt-extruding a thermoplastic polyimide film, or by biaxial stretching The thermoplastic polyimide film is adhered to the metal foil or the conductive loop layer after being heated and pressurized. A preferred embodiment of the method for producing a flexible laminate of the present invention is characterized in that the superposed thermoplastic polyimide film is melt-extruded on the treated side of the roughened or adhesively treated copper foil. a thermoplastic polyimide film prepared after molding, or a biaxially stretched thermoplastic polyimide/resin film, on the opposite side of the film, overlapping at least one of which is roughened or adhesively treated The treated side of the copper foil is then heated and pressurized. Further, a preferred other aspect of the method for producing a flexible laminate of the present invention is characterized in that the thermoplastic polymer is superposed on both sides of the polyimide film which is treated without treatment or double-sided with adhesion treatment. a thermoplastic polyimide film obtained by melt extrusion molding of a quinone imine resin, or a biaxially stretched 10-200806467 (7) thermoplastic polyimide film, and at least one side of the outer surface thereof is roughened The treated side of the treated or adhesively treated copper foil is overlapped inwardly and then heated and pressurized. Further, other preferred embodiments of the method for producing a flexible laminate of the present invention are characterized in that the double-sided flexible substrates which are formed into a loop, have no treatment, or have a double-sided adhesiveness therebetween A film of a thermoplastic polyimide film obtained by melt-extruding a thermoplastic polyimide film or a film of a two-axis-extending thermoplastic polyimide film is then introduced and then heated and pressurized. Further, in another aspect of the method for producing a flexible laminate according to the present invention, it is characterized in that the outer layer of the double-sided flexible substrate which is formed into a circuit, has no treatment, or has a double-sided adhesive treatment is overlapped. a thermoplastic polyimide film obtained by melt-extruding a thermoplastic polyimide film, or a biaxially stretched thermoplastic polyimide film, and then at least one side roughened or densely treated copper The treated side of the foil is overlapped inwardly and then heated and pressurized. In the method for producing a flexible laminate according to any of the above aspects, it is preferred to use a one-side or two-side surface modification treatment as the thermoplastic polyimide film or biaxially stretched thermoplastic. Polyimine resin film. In a preferred and preferred embodiment, the heat and pressure are based on the glass transition temperature Tg of the thermoplastic polyimide resin used, preferably a thermoplastic polyimide film or a biaxially stretched thermoplastic polyimide resin. The film has a glass transition temperature Tg or higher and a temperature equal to or lower than the melting point, more preferably at a temperature of 300 to 380 ° C, and more preferably at the time of the above-described heating and pressing, and is disposed on the heated and pressed material. Between the connected pressure plate and the pressure plate of the press machine -11 - 200806467 (8), the felt-like cushioning material is interposed, preferably a felt buffer material of aromatic polyamine or polybenzoxazole. . [Effect of the Invention] * The flexible laminate of the present invention comprises a metal foil layer/thermoplastic polyimide layer formed by adhering a metal foil layer or a conductor loop layer to at least one surface of the thermoplastic polyimide layer. Or/and a flexible circuit layer of a conductive circuit layer/thermoplastic polyimide layer; in the form of the above thermoplastic polyimine layer, obtained by melt-extruding a thermoplastic polyimide film Since the thermoplastic polyimide film or sheet is formed, a thermoplastic polyimide film having a high purity such as a monomer-free residue or a residual solvent can be used, and a thermoplastic polyimide layer and a metal foil can be provided. The adhesive strength between the layers or/and the conductive loops, or the excellent mobility resistance, and the metal foil/thermoplastic polyimide layer having the excellent heat resistance, electrical properties, and mechanical strength of the polyimide. @Flexible laminate of conductive loop layer / thermoplastic polyimide layer. Further, in other forms, since the above-mentioned thermoplastic polyimide layer is formed of a biaxially stretched thermoplastic polyimide film or sheet, the thermal expansion ratio of the metal foil to be laminated can be provided. There is almost no difference or very small difference, and the adhesion strength or the mobility resistance between the thermoplastic polyimide layer and the metal foil layer or/and the conductive circuit layer is excellent, and in addition to the excellent heat resistance and electrical properties of the polyimide. In addition to the strength of the machine, a metal foil/thermoplastic polyimide layer or/and a conductive loop layer/thermoplastic polyimide layer flexible laminate -12 excellent in dimensional stability and solder heat resistance - 200806467 (9) Board. In particular, the thermoplastic polyimide layer is a biaxially stretched thermoplastic sub-paste obtained by melt-extruding a crystalline polyimine resin obtained by biaxial stretching. When the amine resin film is formed, it is easier to produce a thermoplastic polyimide film i film having high purity such as the above-mentioned impurities such as a single residue or a residual solvent. In addition, the thermal expansion α of any of the MD direction and the TD direction (hereinafter simply referred to as the thermal expansion coefficient) is also in the range of 5xl (T6 to 30 χ 10_6 / Κ (Lu abbreviated as ppm / K), in addition, the MD direction and TD A biaxially stretched thermoplastic polyanthraquinone film having a difference in thermal expansion coefficient of 20 ppm/K can be effectively prevented from shrinking when laminated with a metal foil. Further, the thermoplastic polyimide film is extended by two axes. The glass transition temperature Tg can be higher than the unstretched thermoplastic polyimide resin thin glass transfer temperature Tg by 10 to 8 (TC, which improves solder heat resistance. Further, the flexible laminate of the present invention is produced by plastic polymerization. A thermoplastic polyamine resin film or a biaxially stretched thermoplastic polyimide film obtained by melt-extruding a bismuth imine resin, and a method of heating and pressing a foil or a conductor loop layer, so-called lamination* Since the flexible laminate is manufactured as described above, it is possible to carry out the lamination of a plurality of layers in one step without the occurrence of voids, and it is possible to produce the polyimide having excellent properties at a low cost and at a low cost. Heat resistance, Flexible laminates with strong mechanical strength, or flexible laminates with excellent properties such as excellent sizing, solder heat resistance, etc. Therefore, the flexible double-sided copper layer can be produced with good productivity in a single step. A plywood or thermoplastic polyimide film is embedded as a loop of adhesive thermoplastic imine polythene remnant fat thinner than 20-200 to the imine roll of the glass film to make the thermal sub-metallurgical process Manufacture of a flexible laminated substrate of various multilayer structures utilized in a simple, adhesive layer-13-200806467 (10) (bonding sheet) or interlayer insulating material. Further, in accordance with a preferred embodiment of the present invention The above thermoplastic polyimide layer has a glass transition temperature (Tg) of 180 to 280 ° C, or a extrusion temperature of 30 ° C higher than the melting point of the resin - with a range of 50 to SOOhecT1] The melt viscosity measured by the shear v-cutting speed is 5x1 ο1 to lxl 〇 4 [Pa · S]. Since it is preferably a thermoplastic poly φ imimine resin having a repeating structural unit of the general formula (1) described later, it is preferred to have The thermoplasticity of the repeating structural unit of the formula (5) described later The polyimine resin is more preferably a thermoplastic polyimide resin containing a repeating structural unit of the following formulas (6) and (7), or a thermoplastic having a repeating structural unit of the following formulas (6) and (8); Since the polyimine resin is used, the thermoplasticity of the polyimide resin can be used at a temperature equal to or higher than the glass transition temperature Tg and at a temperature equal to or lower than the melting point, preferably at a temperature of 300 to 380 ° C. The physical state of the melting and hardening is simply laminated, and in particular, the crystalline thermoplastic polyimide resin and the thermoplastic resin which is melted in a lamination processing temperature with II are preferably 280 to 3 in melting point ▲ When a mixture of other thermoplastic resins at 50 ° C is formed, the adhesion strength at the time of lamination can be further improved. Further preferably, during the heating and pressurization, it is preferably disposed between the pressure plate connected to the heated and pressed material and the pressure plate of the press machine, and is preferably an aromatic polymer by interposing a felt-like cushioning material. A felt-like cushioning material of guanamine or polybenzoxazole can obtain a flexible laminated substrate which is smooth and uniform in thickness even in a wide area. [Best Mode for Carrying Out the Invention] -14-200806467 (11) As described above, the flexible laminate of the present invention and the method for producing the same are those obtained by melt-molding a thermoplastic polyimide resin. A method in which a film of an imide resin or a film of a biaxially stretched thermoplastic polyimide film is adhered to a metal foil or a conductor circuit layer by heating and pressurization is carried out by a so-called lamination method. v Prior art In order to form a film-like polyimide layer, since the precursor of the thermoplastic polyimide, Φ polyamine, is imidized on the copper foil or polyimide film by the above, There is a monomer residue or a residual solvent, which is a major cause of a decrease in electrical characteristics. Further, when the pressure is applied by heating, a gap is likely to occur between the layers due to the generation of gas by the impurities, and there is a problem that the coating and heating steps become complicated when laminating. However, a flexible laminate of various structures can be produced by a lamination method according to the present invention by developing a film of a thermoplastic polyimide film which can be melt-formed as described later. The characteristics of the manufacture of the flexible laminate by such a lamination method are as follows. # (1) The thermoplastic polyimide used is a melt-molding process similar to a general plastic material, and the polyimide film is formed by a T-die extrusion method excellent in mass productivity. Employed (2) Since the ruthenium imidization reaction has been completed at the production stage of the resin pellets, it is not necessary to carry out the oxime imidization reaction when the film is formed, and the purity of impurities such as a monomer-free residue or a residual solvent can be used. Thermoplastic polyimide film. (3) It is not laminated by a hydrazine imidization reaction of a polyaminic acid or a resin hardening reaction, and the thermoplasticity of the polyimide resin is utilized, and melting and hardening by pressurization by heating -15 - 200806467 (12) The physical state changes and is laminated. (4) The heating and twisting of the thermoplastic polyimide film is carried out at a temperature of not more than Tg and not more than the melting point in a state where it is not completely melted. (5) When heated and pressurized, it is disposed between the pressure plate and the pressure plate of the press machine connected to the heated and pressed material, and is obtained by using a felt-like cushioning material having heat resistance. Even a wide, smooth and uniform layer of fleshy φ plywood. (6) The substrate forming the loop can be laminated. Further, the method for producing a flexible laminate by the lamination method of the present invention has the following points as compared with the advantages of the prior art method. (1) A circuit board having excellent heat resistance, electrical properties, and mechanical strength which is excellent in polyamidimide can be obtained without using an adhesive having poor heat resistance, etc., so that a wholly polyimine substrate can be produced. (2) Since the thermoplastic polyimide film has high purity, it is excellent in resistance to β mobility. • (3) Lamination of a metal foil or a conductor layer and a thermoplastic polyimide film to obtain a circuit substrate having high adhesion strength. (4) Although the voids of the laminate and the warp caused by the generation of the gas are caused by the lamination of the hydrazine imidation reaction, such a problem does not occur because of the thermoplasticity of the thermoplastic polyimide film. (5) Since only the thermoplastic polyimide film formed by the adhesion is heated, the steps are simple, and by stacking a plurality of layers, lamination of a plurality of layers can be carried out in one step. Further, in a preferred embodiment of the present invention, the biaxially stretched thermoplastic polyimide film is adhered to the metal foil or the conductor circuit layer by heating and pressurization. When a thermoplastic polyimide film is laminated on a metal foil, since it is thermoplastic, the coefficient of thermal expansion is higher than that of the prior art thermosetting polyimide/resin (the thermal expansion ratio of the thermoplastic polyimide resin is 40xl (T6~) 60xl (T6 ^ /Κ ), laminated metal foil with low thermal expansion rate (thermal expansion rate of about 20x1 (Γ6 /Κ), it is easy to produce warpage due to dimensional difference when cooling to room temperature, Φ will be used for manufacturing size The control of lamination conditions of flexible laminates excellent in stability, etc. becomes difficult. As described above, in the technical field of flexible laminates, the requirements for high-density mounting are strict, and when manufacturing precision wiring boards are high, A material excellent in mechanical properties such as dimensional stability, thermal expansion coefficient, and tensile modulus. It is generally used when a thermoplastic plastic film is used for a flexible circuit board, and reflow soldering is performed for mounting a part. The temperature at the glass transition temperature Tg is softened by the film, and warpage or distortion of the warpage or the like is caused on the flexible circuit board. This is a problem in the thermoplastic polyimide film. • For the temperature at which the glass transition temperature Tg is the same as or lower than the processing temperature of the lead-free soldering, heat resistance is required to be improved. The inventors of the present invention have found that crystalline thermoplastics are obtained as a result of further investigation of such phenomena. The polyimide film can be reduced in thermal expansion rate to the copper foil or the same 20ppm/K or near the thermosetting polyimide film by biaxial stretching, and can be extended by two axes. Increasing the glass transition temperature Tg, even if the temperature above 300 ° C remains rigid. That is, the thermoplastic polyimide resin is biaxially stretched, and the thermoplastic -17-200806467 (14) polyimine resin is in the film. The isotropic molecular alignment in the plane direction reduces the coefficient of thermal expansion, and by adjusting the stretching temperature or the stretching speed, it can be adjusted to be reduced to the same thermal expansion ratio as that of the copper foil or the thermosetting polyimide film. In addition, the biaxial extension is followed by heating and fixing (heat-fixing) the molecular alignment while restraining the shrinkage, even if the glass of the thermoplastic polyimide resin before stretching is used. In the temperature region where the temperature Tg is moved, it is not possible to return to the original thermal expansion coefficient, and the temperature can be heated and maintained while maintaining the reduced thermal expansion rate in the temperature range of the glass transition temperature Tg or more and the melting point or lower. The residual stress of the film generated during molding is also removed, and there is no film having excellent dimensional stability after heating/cooling to an adhesive temperature. Therefore, it can be manufactured when laminated on a metal foil or a conductor loop. A laminate having excellent warpage, dimensional precision, and dimensional stability is not produced. Moreover, the glass transition temperature can be increased by subjecting the thermoplastic polyimide film to biaxial stretching, for example, the glass transition temperature Tg is 258 °c. The thermoplastic polyimide resin is raised to 305 ° C by biaxial stretching. By biaxially stretching the thermoplastic polyimide film, the glass transition temperature may rise by 1 〇 to 80 ° C, and the temperature is maintained at a temperature of 300 ° C or more. As a result, even if it exceeds the glass transition temperature Tg before stretching, the film does not start to soften, and when used as a printed circuit board, the solder heat resistance at the time of reflow soldering is also improved. The glass transition temperature is measured and analyzed by the enthalpy test for measuring the coefficient of thermal expansion. Hereinafter, the description will be made with reference to the drawings. -18- 200806467 (15) Figure 1 is a schematic view showing the TMA curve of a thermoplastic polyimide film unstretched film and a thermoplastic polyimide film extended film, as is clear from Fig. 1, by making a thermoplastic poly The amine resin is biaxially stretched to increase the glass transition temperature Tg. Further, the glass transition temperature Tg is a thermal expansion coefficient - a point where the line segment rises gently and the point where the line rises steeply. Next, the biaxial stretching of the thermoplastic polyimide film will be described. The φ extension step is simultaneous with both the biaxial extension and the successive biaxial extension, and the extension temperature is preferably in the range of 250 to 275 t; if the extension temperature is too low, the stress required for the extension is strong and cannot be extended, or the film is extended. Rupture or uneven extension; on the other hand, if the extension temperature is too high, the molecular alignment is small, and the thermal expansion reduction effect due to the extension is not exhibited. Further, the stretching ratio is preferably in the range of 2.5 to 5 times, and the stretching ratio is too low, the molecular alignment is insufficient and the coefficient of thermal expansion is not lowered, or the film is wrinkled during heat setting, and on the other hand, the stretching ratio is too high. Causes problems such as film breakage when stretching #. • In addition, the extension speed is preferably in the range of 100 to 1000%/min, and the extension speed is low, the molecular alignment is small, and the thermal expansion rate is not lowered. On the other hand, the extension speed is limited by the ability of the shovel to extend the device. . Next, the heat setting condition may be at a heating temperature of 280 to 3 80 ° C, preferably 290 to 3 30 ° C, and the shrinkage is limited to 2 to 20%, preferably 4 to 10%, and the time is 1 to 5 Any setting within the range of 000 minutes. If the heat setting temperature is too low, a large dimensional change occurs when the stretched film is heated again, and when the heat setting temperature is higher than the melting point in the other direction, the molecular alignment by extension is eliminated. -19- (16) 200806467 The method of biaxial stretching can use a method of extending with a plurality of rollers, a method of stretching using a tenter, a method of stretching by rolling with a roller, a method of extending a tube type, and the like. A conventional method. In the industry, the stretching method using a tenter is often used, and the second-order segments of different steps are respectively extended in the longitudinal direction and the vertical direction, and simultaneously extended in the direction of the 緃^ direction and the vertical direction, by any method. It is possible to carry out two-axis extension. When φ is successively extended by two axes, the thermoplastic polyimide film to be stretched is first preheated at 250 to 300 ° C, and is uniformly extended to a predetermined temperature in a state of 2 to 5 times; Next, the temperature range of 250 to 300 ° C is extended by 2 to 5 times in one direction in the direction perpendicular to the extending direction. Next, the film is thermally fixed under the temperature range of 280 to 3 80 ° C, and is heat-fixed, and although it is accompanied by the shrinkage of the film after stretching, while maintaining the stretched state of the contraction, the shrinkage is gradually restricted to 2 Cool down to ~20% of the state. Φ At the same time of biaxial stretching, preheating the thermoplastic to be stretched at 250 to 300 ° C. The polyimide film of the polyimide film is simultaneously extended in two directions perpendicular to each other in a state of being uniformly heated to a predetermined temperature λ. 2 to 5 times; then, the film is thermally fixed under extension in a temperature range of 280 to 380 ° C, and is heat-fixed, although accompanied by the shrinkage of the film after stretching, while maintaining the stretched state of the contraction Slowly cool down while limiting the shrinkage to 2 to 20%. By subjecting the thermoplastic polyimide film to biaxial stretching as described above, the thermal expansion of either the MD direction and the TD direction can be made 5 to 30 ppm/K, preferably 10 to 25 ppm/K. In addition, MD Fang-20-200806467 (17) The biaxially stretched thermoplastic polyimide film with a difference in thermal expansion ratio to the TD direction of 20 ppm/K can effectively prevent the metal foil layer Warpage that occurs when pressed. Moreover, by subjecting the thermoplastic polyimide film to biaxially stretching, the glass transition temperature T g can be increased by 10 to 80 ° C higher than the glass transition temperature Tg of the unstretched thermoplastic-polyimine resin film. Solder heat resistance. In addition, even if the thermal history below the melting point is accepted, a low low expansion ratio can be maintained, and excellent dimensional stability and necessary adhesive strength can be maintained, and the laminate is not laminated to copper by selecting appropriate lamination conditions. The resin flows out when the foil is used. The biaxially stretched thermoplastic polyimide film obtained by the above method is in a state of not being completely melted, and the glass transition temperature Tg of the thermoplastic polyimide resin before stretching is preferably Tg or more, preferably a biaxially stretched thermoplastic polymer. The imide resin film has a glass transition temperature Tg or more, a temperature lower than the melting point, preferably 300 to 3 80 °c, and can be easily laminated on a copper foil, a conductor loop layer, a polyimide film, or the like. It is heated on the pressurizing material. The higher the pressure of the layer #, the lower the lamination temperature can be, but generally because the layer-pressure pressure is too high, the resulting laminate will tend to change in size, so the range of 5 to 50 kgf/cm2 is relatively appropriate. The thermoplastic polyimide film before the biaxial stretching may be a thermoplastic polyimide film obtained by melt-molding a thermoplastic polyimide film, or by a casting method as in the prior art. Any of the obtained thermoplastic polyimide film films, in particular, a thermoplastic polyimide film obtained by melt-molding a thermoplastic polyimide resin, can have the following advantages. -21 - (18) (18)200806467 (1) A polyimide film can be formed by a T-die extrusion method excellent in mass productivity. (2) Since the ruthenium imidization reaction has been completed at the production stage of the resin granules, it is not necessary to carry out the oxime imidization reaction when the film is formed, and it is possible to use a thermoplastic having high purity without impurities such as a monomer residue or a residual solvent. Polyimine resin film. (3) Since the thermoplastic polyimide film has a high purity, it is excellent in migration resistance. The material of the thermoplastic polyimide film of the present invention can be used, for example, a thermoplastic polyimide resin or a polyether phthalimide resin, which will be described later, and these may be used alone or in combination of two or more. In addition, in this specification, the term "thermoplastic polyimide resin" is understood to mean a thermoplastic polyimide resin and a polyether phthalimide resin, and the term "thermoplastic polyimide film" means Refers to a polyimide film having a thermoplastic (heat reversibility of hardening and softening). Further, the logarithmic viscosity of the thermoplastic polyimide resin used in the present invention is not particularly limited, but it is generally desirably in the range of about 0.35 to 1.30 dl/g, preferably 0.40 to 1.00 dl/g, and the logarithmic viscosity is low. In the above range, the molecular weight of the resin is small and deteriorates in characteristics. On the other hand, when the content is higher than the above range, the molecular weight of the resin is too large, and the fluidity at the time of extrusion molding is difficult to be obtained, which is difficult. The logarithmic viscosity of the thermoplastic polyimide resin is obtained by dissolving a sample in a mixed solvent of 9 parts by volume of phenol and 1 part by volume of p-chlorophenol (concentration: 0.5 g/dl), and the viscosity of the mixed solvent is ubbelohde The viscometer was measured at 30 ° C and was calculated by the following formula (1). -22- (19) (19)200806467 [Number 1] Logarithmic viscosity = ... Formula (1) [where t is the falling time of the solution (sec), and to is the falling time of the mixed solvent ( Sec ) , C is the solution concentration (g/dl). The thermoplastic polyimine resin may be a repeating structural unit represented by the following general formula (1).

In the above general formula (1), X is a direct bond, -S02_, -CO_, -C(CH3)2-, -C(CF3)2- or -S-, and R1, R2, R3, and R4 are each independently It is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group, a halogenated alkyl group, a halogenated alkoxy group or a halogen atom, and Y is a group selected from the group consisting of the following formula (2).

The thermoplastic polyimine resin having the repeating structural unit represented by the above general formula (1) may be an ether diamine of the following general formula (3) and -23-200806467 (20) the following general formula (4) The polycarboxylic acid obtained by reacting the tetracarboxylic dianhydride as a raw material in the presence or absence of an organic solvent is produced by chemically or thermally hydrazide.

In the above general formula (3), R1, R2, R3 and R4 each have the same meaning as the symbol in the above formula (1).

(4) In the above general formula (4), Y represents the same meaning as the symbol in the above formula (1). In the above general formula (1) and general formula (3), specific examples of R1, R2, R3 and R4 include a hydrogen atom, an alkyl group such as a methyl group or an ethyl group, a methoxy group or an ethoxy group. A halogen atom such as a halogenated alkoxy group such as an oxy group, a fluoromethyl group or a trifluoromethyl group, or a halogenated alkoxy group such as a fluoromethoxy group, a chlorine atom or a fluorine atom is preferably a hydrogen atom. Further, X in the formula is a direct bond, 4〇2-, -CO-, -C(CH3)2-, -C(CF3)2- or -S-, preferably a direct bond, -S〇 2-, -CO-, -C(CH3)2_ 〇-24- (21) (21)200806467 Further, in the above general formula (1) and general formula (4), Y is represented by the above formula (2) Preferably, pyromellitic dianhydride is used as the acid dianhydride. More preferably, the thermoplastic polyimide resin is a thermoplastic polyimide resin having a repeating structural unit represented by the following formula (5).

Further, the thermoplastic polyimine resin having the repeating structural unit represented by the above formula (5) can be purchased from "AURUM" (registered trademark) manufactured by Mitsui Chemicals, Inc. Further, preferred examples of the thermoplastic polyimide resin having the repeating structural unit of the following formulas (6) and (7) are also exemplified.

-25- (7) (22) (7) (22)200806467

In the above formulae (6) and (7), m and n represent the molar ratio of each structural unit (not necessarily a block polymer), and m/n is 4 to 9, more preferably 5 to 9, more Good for numbers ranging from 6 to 9. The thermoplastic polyimine resin having the repeating structural unit of the above formulas (6) and (7) may be prepared by using the corresponding ether diamine and tetracarboxylic dianhydride as raw materials in the presence or absence of an organic solvent. The polylysine obtained by reacting it in the presence of ruthenium is chemically or thermally produced. The specific manufacturing method of these can utilize the conditions of the manufacturing method of the conventional polyimine. In the present invention, it is preferred to use a thermoplastic polyimide resin having a repeating structural unit represented by the following formula (8) instead of the repeating structural unit represented by the formula (1) of > ± _ A mature plastic polyimine resin, or combined with the resin. Further, it is also preferable to use a copolymer having a monomer having a structural unit represented by the above formula (1) and a monomer having a structural unit of the following formula (8) + ^ cadmium/T. In the above formula (61, Ό) m, the repeating structural unit of 7κ and the repeating structure represented by the following formula (8) have a ratio of 1:0 to 0.75: 0.25. -26- 200806467

ο

The thermoplastic polyimine resin having a repeating structural unit represented by the following formula (8) can be obtained by using the corresponding ether diamine and tetracarboxylic dianhydride as raw materials in the presence or absence of an organic solvent. The polylysine obtained in the reaction is produced by chemically or thermally hydrazide. The specific manufacturing method of these can utilize the conditions of the manufacturing method of the conventional polyimine. The polyether quinone imine resin may, for example, be a repeating structural unit represented by the above general formula (9). Ο II /°\ / •M D-0 - ZO - D: XC II 0 i? Ν—Ε— (9) In the above general formula (9), D is a trivalent aromatic group, and both are 2 The residue of the price. The polyether fluorene resin having the repeating structural unit of the above general formula (9) can be reacted by using the corresponding ether diamine and tetracarboxylic dianhydride as raw materials in the presence or absence of an organic solvent. The obtained poly-27-200806467 (24) Amine acid' is chemically or thermally subjected to hydrazine imidization to produce a specific production method, and a known polyimine product can be used. Specific examples of the polyether quinone imide resin include, for example, a polyether quinone imine resin having one or more repeating structural units represented by the repeating structural unit represented by the general formula (1〇) to (12). . The strips of these methods are selected from the following

(10) (11) (12) In the above general formulas (10) to (12), the symbol E is a divalent aromatic residue such as a group. -28- (25) 200806467 Pu-Ling, Pu,

A particularly preferred polyether oximine resin to be used is a polyether fluorene imine resin having a repeating structural unit represented by the following formula (13).

The polyether oxime resin having a repeating structural unit represented by the following formula (13) is commercially available from ULTEM (registered trademark) manufactured by GE. The diamine or the tetracarboxylic dianhydride which is a raw material of the thermoplastic polyimine resin as described above may be used singly or in combination of plural kinds, and other copolymerizable components may be contained in a range not inhibiting the object of the present invention. The plural polyimine resin obtained from different monomers can be used by blending the polymer arbitrarily within the range not inhibiting the object of the present invention. The thermoplastic polyimide resin used in the present invention may be added with other resins, and may contain a polyamidamide resin, preferably a wholly aromatic polyamide resin, or a polyfluorene, for example, within a range not inhibiting the object of the present invention. Amine amide resin, polyarylate resin, polyether nitrile resin, polyphenylene sulfide resin, polyether eucalyptus -29 - 200806467 (26) Lipid, polyether ether ketone resin, liquid crystal polymer, and the like. In particular, the crystalline thermoplastic polyimide resin is preferably a mixture of another thermoplastic resin having a melting point of 280 to 350 ° C, and another thermoplastic resin which is molten at a lamination processing temperature. In time, the adhesion strength at the time of lamination can be further improved. • The thermoplastic polyimide film of the present invention can further contain a coloring agent, a releasing agent, various stabilizers, a plasticizer, a lubricant, and various inorganic fillers within the scope of the object of the invention. Additives such as agents and oils. The melt viscosity which can be thinned by extrusion molding is 5×101 to 1χ104 [Pa · S], preferably 4×10 2 to 3×10 3 [Pa · S], and when the melt viscosity is lower than 5×1 01, it is spouted from the die. The subsequent draw do wn is remarkable and the film cannot be produced. On the other hand, when the melt viscosity exceeds 1x1 〇 4 [Pa· S], the load applied to the extrusion screw during melting is large, or it is difficult to spit out from the die. It is impossible to manufacture a film. Next, the manufacturing steps of the thermoplastic polyimide film will be described. w The polyimide film of the present invention can be produced by a melt extrusion molding method to produce, for example, particles or powder of a polyimide resin.

A Other resins and additives as desired 'drying and mixing with a two-axis mixing extruder after a dry mixing such as a Henry's mixer or a ribbon blender' will be used The pressed strands are cooled in water, and the grit of the mixture is cut off, and then the obtained pellets are dried by heating to remove the adsorbed moisture, and then heated and melted by a uniaxial or biaxial screw extruder. The T-die provided at the front end of the extruder is sputtered in a flat film shape. 'Connected or pressed -30- 200806467 (27) Cooled on the roller and hardened to obtain a polyimide film. In addition, without mixing, A method of directly extruding particles or powder is also possible. The thickness of the thermoplastic polyimide film is not particularly limited and is generally from 1 m to 1 mm, preferably from 20/m to 400 m/m. The polyimine resin film generally used is obtained by performing a dehydration condensation reaction on a roller or a base film after casting a solution containing poly-proline, so that the monomer during polymerization or The solvent remains, accompanied by a decrease in electrical properties or φ transparency. On the other hand, regarding the thermoplastic polyimide film, it is necessary to carry out a particle production step by kneading extrusion before performing the T die extrusion molding. After the step of the polymerization reaction and the dehydration condensation reaction, the monomer residue and the solvent remaining in the polyimide resin are removed, and the material of the polyimide resin can be sufficiently utilized in order to be removed during the melt-kneading at the particle production step. Electrical properties or mechanical strength, as well as a highly transparent thermoplastic polyimide film. # The thermoplastic polyimide film prepared as described above, as described above, was further biaxially stretched to obtain a biaxially stretched thermoplastic polyimide film of the present invention. A thermoplastic polyimide film prepared by a T-die extrusion method as described above, or a biaxially stretched thermoplastic polyimide film, and a copper foil or conductor layer, or a usual polyimide resin When the film is pressure-bonded, the adhesion strength can be further improved by modifying the surface of the film. The surface modification method may be a general surface treatment such as corona discharge treatment, or plasma treatment, ozone treatment, excimer laser treatment, alkali treatment, etc., from -31 to 200806467 (28) cost or treatment effect It is better to use corona discharge treatment and plasma treatment. Next, several aspects of the flexible laminated substrate obtained by the method of the present invention will be described with reference to the drawings, but the present invention is not limited to the following forms, and various forms are possible. ^ First, Fig. 2 and Fig. 3 show two structures of a flexible double-sided copper-clad laminate. φ The flexible double-sided copper-clad laminate shown in Fig. 2 is laminated on the treated side of the copper foil 2 which has been subjected to rough surface treatment or adhesion treatment on at least one side, and overlaps the above thermoplastic polyimide film (or two axes) Extending the thermoplastic polyimide film) 1, on the opposite side of the thermoplastic polyimide film (or biaxially stretched thermoplastic polyimide film) 1, overlapping at least one side of the rough surface or dense The treated side of the inventive copper foil 2 is obtained by heating and pressurizing. Alternatively, the thermoplastic polyimide film (or the biaxially stretched thermoplastic polyimide film) 1 is superposed on the treated side of the copper foil 2 which has been subjected to the rough surface treatment or the adhesion treatment at least one side, and is heated. The pressurized two layer ^ can also be constructed. On the other hand, the flexible double-sided copper-clad laminate shown in Fig. 3 is formed by laminating the above-mentioned thermoplastic polyimide film on the surface of the polyimide film 3 which has no treatment or double-sided adhesion treatment. An amine resin film (or a biaxially stretched thermoplastic polyimide film) 1 is further coated on the outer side with at least one side of the treated side of the roughened or adhesively treated copper foil 2, by heating Get it by pressure. Next, Fig. 4 shows a form in which a thermoplastic polyimide film (or a bis-32-200806467 (29) axially stretched thermoplastic polyimide film) is used as an adhesive layer embedded in a circuit. The multilayer flexible laminate is formed with a conductive circuit layer 4 on both sides of the polyimide film 3, and the double-sided flexible laminates which are treated without treatment or double-sided adhesive treatment are interposed therebetween. A thermoplastic polyimide film (or a biaxially stretched thermoplastic polyimide film) 1, ^ is obtained by heating and pressurizing. Finally, Fig. 5 shows a form in which a thermoplastic polyimide film (or a two-φ-axis extended thermoplastic polyimide film) is used as an interlayer insulating layer in which a circuit is buried. The multilayer flexible laminate is formed by forming a conductive circuit layer 4 on both sides of the polyimide film 3, and the outer sides of the double-sided flexible laminates which are not treated or double-coated with adhesion treatment are overlapped a thermoplastic polyimide film (or a biaxially stretched thermoplastic polyimide film) 1, and at least the treated side of the roughened or adhesively treated copper foil 2 is superposed on the inside, heated Obtained by pressurization. Further, the thermoplastic polyimide film of the present invention or the biaxially stretched # thermoplastic polyimide film may also be used as the following application examples. (1) It is used as a coverlay film of various flexible substrates or planar heat generating bodies. (2) It may be laminated with a metal foil of copper, stainless steel, aluminum, nickel, etc., preferably as a laminate with copper foil, and further, by using a metal paste or metal on the surface of the metal foil The bumps are used to penetrate the insulating layer (the thermoplastic polyimide film or the biaxially stretched thermoplastic polyimide resin), and the interlayer connection can be simultaneously performed. (3) Multi-layer lamination can be performed at one time, and lamination can be performed in one step. -33- (30) 200806467 (4) The layers may be laminated one by one, for example, by sequentially using Tg different thermoplastic polyimide film or biaxially stretched thermoplastic polyimide resin, and successive lamination may be employed. Further, by laminating a thin Tg-high thermoplastic polyimide film or a biaxially stretched thermoplastic polyimide resin, a TG low thermoplastic polyimide film or a biaxial extension is sequentially laminated. * The stretched thermoplastic polyimide resin is thin, although it has the limitation of the number of laminations, it can be laminated one by one. [Embodiment] The present invention is specifically described by the following examples, but the present invention is not limited to the embodiments, and the present invention can be based on those skilled in the art without departing from the scope of the invention. Knowledge is implemented in various forms of improvement, change, and revision. Production Example 1 of a Thermoplastic Polyimine Resin Film Using a Chemical Structural Formula at a Ratio of 90:10 to the above (6)

* (7) Thermoplastic polyimine (AURUM' (registered trademark) PD500A by Mitsui Chemicals Co., Ltd.; Tg25 8 [t:], melting point 3 80 [it], measured at a shear rate of 500 secT1 Melt viscosity 700 [Pa · S]), and thermoplastic polyimine of the above formula (6) (Aurum (registered trademark) PD450C manufactured by Mitsui Chemicals Co., Ltd.; Tg250 [t:], melting point 3 80 [t:], the resin particle of the melt viscosity of 5 〇〇 [Pa · S] measured by the shear rate of SOOsecT1, and the melt viscosity of the thermoplastic polyimide resin used for extrusion molding [pa · S], measured according to JIS K-7199, using -34- 200806467 (31) Shimadzu FLOW TESTER CFT-500. After drying the above resin pellets at 180 ° C for 10 hours in a hot air type high temperature bath, a spiral diameter of 50 mm is used. The uniaxial extruder is pressed against the T die provided at the front end thereof, and the film extrusion temperature is 42 0 ° C. After the resin material is discharged from the T die, the temperature is adjusted to 220 T: cooling. The roller is cooled and hardened, and the corona discharge treatment is performed on both sides to obtain a thermoplastic polythene having a thickness of 50 // m. A resin film (hereinafter, referred to as a thermoplastic film PI a). Further, in the case of φ, the corona discharge treatment on the surface of the film was carried out under the conditions of a tile density of 120 W/m 2 /min using a corona treatment apparatus manufactured by Ba Industrial Co., Ltd. Production Example 2 of a thermoplastic polyimide film: Aurethane (Mitsubishi Chemical Co., Ltd.) having a chemical structure of the above formula (6) and (7) was used in a ratio of 9 〇:10 (registered) Trademark) PD500A; Tg25 8 [°C], melting point 380 [°C], melt viscosity measured at a shear rate of 500 secT1 ([Pa · S]), and chemical formula (13) The resin pellet of the thermoplastic polyether phthalimide (ULTEM 1 000P, manufactured by General Electric Company) was obtained by the same method and corona discharge treatment as in the above-mentioned thermoplastic polyimide film of the thermoplastic polyimide film to obtain a thickness of 50 // A thermoplastic polyimide film of m (hereinafter referred to as thermoplastic PI film b). Polyimine resin film: The chemical structure is the polyimine of the above formula (7) because a film of a polyimide resin is generally sold (Tongli Dubang Co., Ltd. -35- (32) (32) )200806467

Kapton 200H), so the commercially available polyimide film was used. Further, the polyimide resin is a linear polymer which does not have thermoplasticity (thermal reversibility between hardening and softening) and cannot be separately extruded. Therefore, the commercially available polyimide film (hereinafter also referred to as PI film) is subjected to a dehydration condensation reaction by casting a solution of a precursor containing polylysine onto a roller or a flat surface. Get the winner. Example 1 A copper foil having a thickness of 18/m was superposed on both sides of a 50/zm thermoplastic PI film a, and was sandwiched from a stainless steel plate (referred to as SUS) on both sides thereof, and on both sides of the SUS plate, FUJIRON STM, manufactured by FUJICO, which is a felt-like cushioning material made of polybenzoxazole, was placed in a vacuum high-temperature press machine manufactured by Kitagawa Seiki Co., Ltd., and then depressurized to 1.0 kPa. The pressure of the pressure l〇kgf/cm2 is raised by 5 ° C / min. After the temperature is raised to 300 ° C, the pressure is increased to 25 kgf / cm 2 of the secondary forming pressure, and maintained for 1 minute in this state, and then slowly cooled. At room temperature, the flexible double-sided copper-clad laminate substrate shown in Fig. 2 was obtained. Using the obtained copper-clad laminate, the characteristics shown in Table 1 were evaluated, and the results are shown in Table 1. Example 2 A flexible double-sided copper-clad laminate which was obtained in the same manner as in Example 1 except that the pressurization temperature in Example 1 was changed to 340 ° C, and the obtained copper paste was used. The results of the properties evaluated by the laminates are listed in Table 1. -36- (33) (33)200806467 Example 3 The same procedure as in Example 1 was carried out except that the pressurization temperature in Example 1 was changed to 3 60 ° C to obtain a desired flexible double-sided copper layer. The results of the plywood and the properties evaluated using the obtained copper clad laminate are shown in Table 1. Example 4 The same procedure as in Example 1 was carried out except that the pressurization temperature in Example 1 was changed to 380 ° C, and a desired flexible double-sided copper-clad laminate was obtained, and the obtained copper-clad layer was used. The results of the properties evaluated by the plywood are shown in Table 1. Example 5 The buffer material was changed to P-ARAMID (aromatic polyamide, (manufactured by FU1ICO, trade name), except that the pressurization temperature in Example 1 was changed to 3 3 0 t and 380 °C. The same results as in Example 1 were carried out except for FUJIRON 9000"), and the desired flexible double-sided copper-clad laminates were obtained. The results of evaluation of the properties evaluated using the obtained copper-clad laminates are shown in Table 1 - 37- (34) 200806467 [Table l] Pressurization conditions and characteristics Example 1 2 3 4 5 Pressurization temperature (.〇300 330 360 380 330 380 Buffer material PBO PBO PBO PBO P-ARAMID Buffer material 沾〇〇Δ Peel strength (N/cm) Thermoplastic PI film a-copper foil 14 13 14 14 13 14 Solder heat resistance good and good good resin oozing ◎ BOPBO: polybenzoxazole (trade name) "FUJIRONSTM", manufactured by FUJICO) P-ARAMID: Aromatic polyamide (trade name "FUJIRON 9000", manufactured by FUJICO) It is clear from the results shown in Table 1 that the thermoplastic of the present invention is used. In the PI film, even at any temperature of the pressurization temperature of 3 3 0 to 3 0 0 °c, there is no Adhesive or resin bleed out of the punched material, excellent adhesion to copper foil at high peel strength, and excellent soldering heat resistance. Moreover, only a few sticks are used because of the use of a buffer material made of aromatic polyamide. In the case of using a felt-like cushioning material made of polybenzoxazole as a cushioning material, it is preferred.

Further, in the same manner as in Example 1, except that the pressurization temperature in Example 1 was changed to 250 ° C, there was no problem with the adhesion of the cushioning material or the resin bleeding, but the peeling strength was rather low, and The soldering heat resistance is also not good, so it is desirable to pressurize the temperature above 300 °C. On the other hand, as a result of changing the pressurization temperature to 400 ° C, the other characteristics were the same as those of Example 1, but the bleeding of the resin was observed. Therefore, when a thermoplastic PI film was used, the pressurization temperature was desired. Below 400 °C. In addition, in the third embodiment, the FUJIRON STM on both sides of the SUS plate as the cushioning material is changed to the FUJIR0N-38-(35) 200806467 6 000 cushioning material manufactured by m-ARAMID Co., Ltd., and the third embodiment is the same as the third embodiment. As a result of the same, the other characteristics were the same as those of Example 3, but the adhesion of the cushioning material was observed. Regarding the characteristics shown in the above Table 1, the evaluation was performed as follows (the latter is also the same as Table 2 to Table 5). (1) Adhesion of cushioning material • Whether or not the cushioning material used for heating and pressurizing is adhered to the SUS plate or the body of the presser, and after visual inspection, it is visually judged. 〇: no stickiness △: only a small amount of sticking X: sticking (2) peeling strength The peeling strength of the obtained flexible double-sided copper clad laminate _ (N / cm), measured according to JIS C 6 8 4 1 . (3) Soldering heat resistance The obtained flexible double-sided copper-clad laminate was floated in a solder bath at 260 ° C for 1 〇 second to bring the copper foil side into contact with the solder bath. After cooling to room temperature, visually observe whether there is any Swelling or peeling, judging the pros and cons. (4) Resin exudation After the flexible double-sided copper-clad laminate having a predetermined size was pressed, the amount of exudation of the polyimine resin from the end portion was visually judged to be -39-(36) 200806467. ◎: no bleed out: only a small amount of bleed x: a large amount of bleed out Comparative Example 1 A commercially available resin (kapton 制 manufactured by Toray Dupont Co., Ltd.) which was produced by extrusion molding but not by the extrusion method, and thermoplastic example 1 The flexible circuit board production (pressurization) condition is not normal, and adhesion to the copper foil cannot be performed. Further, in the temperature of 400 ° C or higher, the flexible circuit board production (pressurization) condition of Comparative Example 2, polyethylene naphthalate produced in the extrusion molding example 1 was also impossible. Sexual, but unable to adhere to the copper foil. Example 6 A thermoplastic film of 5 0 /X m (a thermoplastic foil of a thickness of 15/zm and a copper foil having a thickness of 18/zm on both sides of Toray DuPont (20H), SUS from both sides thereof On the both sides of the SUS plate, FUJIRON is used as a cushioning material in a vacuum high-temperature press machine manufactured by Kitagawa Seiki Co., Ltd., and then at a pressure of 1.0 kPa, at a pressure of 初期kgf/cm2 at an initial pressure of yttrium. Does not exist to show the flow of squatting. The film, with a little flow) made of kapton PI film, and STM, device, decompression temperature 5 〇C / mi η · -40- 200806467 (37) After the temperature reached 300 ° C, the pressure was raised to the secondary state for 10 minutes, and then slowly extended to the flexible double-sided copper-clad laminate shown in FIG. The slabs were evaluated for the characteristics shown in Table 2. In the same manner as in Example 6, except that the pressurization temperature in Example 6 was carried out in the same manner as in Example 6, the results were obtained, and the obtained copper clad laminates were used for listing. In Table 2. (Example 8) The same conditions as in Example 6 were carried out except that the pressurization temperature in Example 6 was carried out, and a target was obtained, and the obtained copper-clad laminate was shown in Table 2. The pressure was 25 kgf/cm2, and after cooling to room temperature, the obtained copper layer was used as shown in Table 2. More than 3 3 ° C, the results of the evaluation of the flexible double-sided copper lamination evaluation are more than 3 60 ° C, the results of the characteristics of the flexible double-sided copper lamination evaluation - 41 - (38) 200806467 [Table 2] Pressurization conditions and characteristics Example 6 7 8 Pressurization temperature (.〇300 330 360 Buffer material PBO PBO PBO Buffer material phase 5 peel strength (N/cm) PI film-thermoplastic PI film a cannot be measured* (material damage) Unmeasured* (material damage) Unmeasured* (material damage) 13 Thermoplastic enamel film a-copper foil 14 14 Solder heat resistance good resin oozing ◎ 〇〇 PBO: Polybenzoxazole (trade name "FUJIRONSTM", (stock) FUJICO) * Material damage: Because the adhesion strength is too strong, the interface cannot be peeled off during the peeling test and the result is shown in Table 2 above. It is clear that when the thermoplastic PI film of the present invention is used, even at any temperature of the pressurizing temperature of 330 to 3 60 ° C, there is no sticking of the cushioning material or resin bleeding, and adhesion to the copper I fg at a high peeling strength. Excellent in properties and excellent in soldering resistance. In the same manner as in Example 6, except that the pressurization temperature in Example 6 was changed to 25 〇t: -, the viscous of the cushioning material, the stickiness of the adhesive or the resin, and the peeling of the resin were not problematic, but peeling off. The strength is relatively low, and the solder heat resistance is also poor, so it is desirable to pressurize the temperature above 300 ° C. On the other hand, the result of changing the pressurization temperature to 400 ° C is the same as the other examples. No problem, but bleed out of the resin was observed, so when using a thermoplastic PI film, it is desirable to pressurize the temperature below 400 ° C. Example 9 - 42 - (39) (39) 200806467 50 / / m thermoplastic pi film A two-layer flexible polyimine double-panel having a conductor loop is overlapped on both sides of a, and the FUJIRON STM device is used as a cushioning material on both sides of the SUS plate. The vacuum high-temperature press machine made by the fine machine (stock) is then subjected to a pressure reduction to 1.0 kPa, and the temperature is raised to 5 ° C/min at an initial pressure of 10 kgf/cm 2 · the temperature is raised to 3 60 ° C, and the pressure is increased to two. The secondary forming pressure is 25 kgf/cm2, and it is kept for 10 minutes in this state, then slowly enters After cooling to room temperature, a multilayer flexible double-sided copper-clad laminate in which the conductor loop layer shown in Fig. 4 was embedded in a thermoplastic PI film was obtained. Using the obtained copper-clad laminate, the characteristics as shown in Table 3 were evaluated. The results are shown in Table 3. Example 1 The same procedure as in Example 9 was carried out except that the pressurization temperature in Example 9 was changed to 3 30 ° C, and the desired multilayer flexible double-sided sticker was obtained. The results of the copper laminates regarding the properties evaluated using the obtained copper-clad laminates are shown in Table 3. Example η In the same manner as in Example 9, except that the pressurization temperature in Example 9 was changed to 360 ° C, the obtained multilayer flexible double-sided copper-clad laminate was used, and the obtained copper-clad layer was used. The results of the properties evaluated by the plywood are shown in Table 3. -43- (40) 200806467 [Table 3] Force [] Pressure Conditions and Characteristics Example 9 10 11 Pressurization Temperature (.〇300 330 360 Buffer Material PBO PBO PBO Buffer Material Peel Peel Strength (N/ Cm) PI film thermoplastic PI film a cannot be measured* (material damage) cannot be measured* (material damage) cannot be measured* (material damage) thermoplastic PI film a-conductor loop layer 14 14 13 circuit buried good good solder heat Good good resin oozing ◎ 〇〇 Preparation PBO: Polybenzoxazole (trade name "FUJIRONSTM", (stock) FUJICO) * Material damage: Because the adhesion strength is too strong, the interface cannot be peeled off during the peel test and cause damage. From the results shown in the above Table 3, it is clear that when the thermoplastic PI film of the present invention is used, even at any temperature of the pressurization temperature of 3 3 0 to 360 ° C, there is no sticking of the cushioning material or resin bleed out, and the circuit is buried. It is excellent in both solderability and solder heat resistance, and is excellent in adhesion to a conductor circuit layer at a high peeling strength. The same as Example 9 except that the pressurization temperature in Example 9 was changed to 250 °C. As a result, there is no problem with the sticking of the cushioning material or the exudation of the resin, but the peeling strength is relatively low, and the circuit embedding property and the soldering heat resistance are also poor, so it is desirable to pressurize the temperature above 300 °C. On the other hand, as a result of changing the pressurization temperature to 400 ° C, the other characteristics were the same as those of Example 9, but the bleeding of the resin was observed, so when the thermoplastic PI film was used, it was desirable to have a low pressurization temperature. 400-44 - (41) 200806467 〇C. The circuit embedding property shown in Table 3 above is evaluated as follows (the same applies to Table 4 to be described later). ★ (5) Circuit embedding property, produced The multilayer flexible double-sided copper-clad laminate was subjected to cross section, and the resin embedding property between the circuits was confirmed by an optical microscope to judge its advantages and disadvantages. Example 1 2 Two-layer flexible polyimine double-panel forming a conductor loop on both sides On both sides, a thermoplastic PI film a and 18/zm copper foils each having a thickness of 50/zm are stacked on the double-sided SUS plate, and the FUJIRON STM is used as a cushioning material on both sides of the SUS plate. Vacuum high temperature pressurization made of fine machine Then, the pressure is reduced to 10 kgf/cm2, and the temperature is raised to 5 ° C /min at an initial pressure of 1 〇 MPa. After the temperature is raised to 360 ° C, the pressure is increased to 25 kgf/cm 2 of the secondary forming pressure. The state was maintained for 1 minute, and then slowly cooled to room temperature to obtain a multilayer flexible double-sided copper-clad laminate in which the conductor/circuit layer shown in Fig. 5 was embedded in a thermoplastic PI film a. Using the obtained copper-clad laminate, the characteristics as shown in Table 4 were evaluated, and the results are shown in Table 4. Example 1 3 The same procedure as in Example 12 was carried out except that the pressurization temperature in Example 12 was changed to 33 (rc), and the desired multilayer flexible double-sided adhesive-45-(42) 200806467 copper laminate was obtained. The results of the properties evaluated using the obtained copper-clad laminates are shown in Table 4. Example 1 4 Except that the pressurization temperature in Example 12 was changed to 3 60 ° C, the same as in Example 12 The same procedure was carried out to obtain a flexible double-sided copper-clad laminate, and the results of evaluation of the properties evaluated using the obtained copper-clad laminate were shown in Table 4. [Table 4] Pressurization conditions and characteristics Example 12 13 14 Pressurization temperature (.〇300 330 360 cushioning material PBO PBO PBO cushioning material peeling strength (N/cm) PI film-thermoplastic PI film a cannot be measured* (material damage) cannot be measured* (material Destruction) Unable to measure* (Material damage) Thermoplastic PI film a-conductor circuit layer 14 13 13 Good embedding of good resistance to soldering heat Good resin exudation ◎ Preparation for test PBO: Polybenzoxazole (trade name " FUJIRONSTM", (share) FUJIC O system) * Material damage: Since the adhesion strength is too strong, the interface cannot be peeled off in the peeling test to cause damage. From the results shown in Table 4 above, it is clear that the thermoplastic PI film of the present invention is used even at the pressurization temperature. 3 3 0~3 Any temperature at 60 °C, no sticking of the buffer material or resin bleed, in addition, the circuit embedding, solder heat resistance -46 - 200806467 (43) are excellent, at high peel strength and conductor The adhesion of the circuit layer was also excellent. The results of the same procedure as in Example 12 except that the pressurization temperature in Example 12 was changed to 250 ° C, the adhesion of the cushioning material or the bleeding of the resin were all There is no problem, but the peeling strength is quite low, and the I-buried property and the soldering heat resistance are not good. Therefore, it is desirable to pressurize the temperature above 300 ° C. On the other hand, the pressurization temperature is changed to 400 ° C. As a result, the properties of φ were the same as those of Example 12, but the bleeding of the resin was observed, so when a thermoplastic PI film was used, it was desirable that the pressurization temperature was lower than 40 ° C. Example 15 The thermoplastic in Example 1 The flexible polyimide film b was changed to the thermoplastic PI film b, and the same procedure as in Example 1 was carried out to obtain a desired flexible double-sided copper-clad laminate, and the obtained copper-clad laminate was used for evaluation. The results are shown in Table 5. Example 16 The same procedure as in Example 15 was carried out except that the pressurization temperature in Example 15 was changed to 3 30 ° C, and the intended purpose was obtained. The results of the properties of the flexible double-sided copper-clad laminates evaluated using the obtained copper-clad laminates are shown in Table 5. Example 17 47-200806467 (44) The same procedure as in Example 15 was carried out except that the pressurization temperature in Example 15 was changed to 360 ° C, and the desired flexible double-sided copper-clad laminate was obtained. The results of the properties evaluated by the obtained copper-clad laminates are shown in Table 5. Example 1 8 A flexible double-sided copper-clad laminate which was obtained in the same manner as in Example 15 except that the pressurization temperature in Example 15 was changed to 380 ° C, was obtained by using The results of the properties evaluated for the copper-clad laminates are shown in Table 5. Example 1 9 In addition to changing the pressurization temperature in Example 15 to 330 ° C and 380 ° C, the buffer material was changed to P-ARAMID (Aromatic Polyamide, manufactured by FUJICO, trade name "FUJIR0N 9000". The results of the characteristics of the flexible double-sided copper-clad laminates obtained in the same manner as in Example 15 except for the evaluation of the obtained copper-clad laminates are shown in Table 5 〇-48. - (45) 200806467 [Table 5] Pressurization conditions and characteristics Example 15 16 17 18 19 Pressurization temperature (.〇300 330 360 380 330 380 Buffer material PBO PBO PBO PBO P-ARAMID Buffer material 沾〇〇Δ Peel strength (N/cm) Thermoplastic PI film b-copper foil 13 13 14 14 13 14 Solder heat resistance good and good good resin oozing ◎ BOPBO: polybenzoxazole (trade name) "FUJIRONSTM", manufactured by FUJICO) P-ARAMID: Aromatic polyamide (trade name "FUJIRON 9000", manufactured by FUJICO) It is clear from the results shown in Table 5 that the thermoplastic PI of the present invention is used. When film b is used, even at any temperature of the pressurization temperature of 3 3 0 to 3 80 ° C, Adhesion without buffer material or resin bleed, excellent adhesion to copper foil at high peel strength, and excellent solder heat resistance. Example 1 of extended film production The thermoplastic structure of the above (6) Amine (registered trademark) PD450C manufactured by Mitsui Chemicals Co., Ltd.; Tg25 0 [°C ], melting point 3 8 8 [t ], melt viscosity measured at a shear rate of SOOsecT1 500 [Pa · S]) After the granulated resin material is dried, the water is removed, and then heated and melted by a uniaxial screw extruder, and discharged from a T-die provided at the front end of the extruder in a flat film form to be in contact with the cooling roller. The film was cooled and hardened to obtain a film (A) of a thermoplastic polyimide film (hereinafter abbreviated as TPI).

The obtained thermoplastic polyimide film (A) is heated at 260 ° C -49-(46) (46)200806467, and the stretching film is obtained by performing a 3-fold stretching operation in two directions perpendicular to each other. The heat-fixing operation was carried out at 300 ° C in an extended state to obtain a biaxially stretched thermoplastic polyimide film (A-3 ) for the purpose, and the same operation was carried out except for stretching twice to prepare a biaxially stretched thermoplastic. Polyimine resin film (A-2). Further, "-3" of (A-3) is a mark added for easy determination of the 3-fold extension, and "-2" of (A-2) is a mark added for easy judgment of a 2-fold extension. (The same is true below). Stretch Film Production Example 2 AURUM (registered trademark) PD500A manufactured by Mitsui Chemicals Co., Ltd.; Tg25 8 [Tylon Chemicals Co., Ltd.] was used in a ratio of 1:1 in a chemical composition of the above formula (6) and (7). °C], a melting point of 38 ° [ ° C ], a granulated resin material having a melt viscosity of 700 [Pa·S] measured at a shear rate of SOOsec T1, and the film shown in Film Production Example 1. The same operation is carried out to obtain a thermoplastic polyimide film (B), and the obtained thermoplastic polyimide film (B) is heated at 260 1 to perform a 3-fold stretching operation in two directions perpendicular to each other. The obtained stretched film was heat-fixed at 300 ° C in an expanded state to obtain a desired biaxially stretched thermoplastic polyimide film (B-3 ). Extension film production example 3 except that the thermoplastic polyimine of the above formula (6) (Aurum (registered trademark) PD450C manufactured by Mitsui Chemicals Co., Ltd.) and -50-200806467 (47) have the chemical structural formula described above. The polyether ether ketone resin of the formula (9) (manufactured by Victrex-MC Co., Ltd., trade name "45 0P") has a ratio of 80:20 to a granulated resin material. The same operation as the film production step shown in Fig. ' yields a thin thermoplastic polyimide film, film (C). The obtained thermoplastic polyimide film (C) was heated at 260 ° C, and stretched three times in two directions perpendicular to each other, and the stretched film obtained by φ was stretched at 300 ° C. The heat-fixing operation gives the intended biaxially stretched thermoplastic polyimide film (C-3). Extended Film Production Example 4 Corona discharge treatment was performed on both sides of a biaxially stretched thermoplastic polyimide film (A-3) prepared in accordance with the above Film Production Example 1, to obtain a biaxially stretched thermoplastic polyimide. Further, the resin film (D-3) was subjected to a corona discharge treatment on the surface of the film, and was carried out under the conditions of a tile density of 120 W/m2 per minute using a battery manufacturing apparatus. In the case of the film production example 5, a granulated resin material having a chemical structure of the above-mentioned (6) thermoplastic polyimine (AURUM (registered trademark) PD450C manufactured by Mitsui Chemicals Co., Ltd.) was used. The film forming step shown is the same operation to obtain a polyimide film (A). The obtained thermoplastic polyimide film (A) was heated at 280 ° C to perform a 3-fold stretching operation in two directions perpendicular to each other, and the stretched film obtained in -51 - 200806467 (48) was 3 1 The heat-fixing operation was carried out at 0 ° C in an extended state to obtain a biaxially stretched thermoplastic polyimide film (E-3 ) for the purpose. Extended Film Production Example 6 ^ Using a granulated resin material having a chemical structure of the above-mentioned (6) thermoplastic polyimine (AURUM (registered trademark) PD450C manufactured by Sanwa Chemical Co., Ltd.), and film production The film production step of the film shown in Example 1 was carried out in the same manner to obtain a thermoplastic polyimide film (A). The obtained thermoplastic polyimide film (A) was heated at 26 Torr, and the stretching film was subjected to a heat stretching operation at 300 ° C in an extended state by performing a 3-fold stretching operation in only one direction. A shaft-extending thermoplastic polyimide film (F-3) is obtained for one of the purposes. The thermal expansion ratio (2 2 〇 -2 〇〇 and the glass transition temperature (Tg) before and after the stretching of the thermoplastic polyimide film extending film obtained in the above-mentioned stretched film production examples 1 to 6 are summarized in Table 6. Further, For reference, the data of the Φ unstretched thermoplastic polyimide film (A) is also listed, and the coefficient of thermal expansion 'uses the line formed by the point of the shape of the secondary element of the film. The rate (CTE) was measured by the following method. In addition, the glass transition temperature (Tg) was determined by the following measurement method by thermomechanical analysis (TMA). <Linear expansion ratio (CTE)> Using the heat of Shimadzu Corporation The mechanical measuring device TMA-60 measures the thermal expansion rate of 20 to 200 ° C at a heating rate of 5 ° C / min under a tensile load of 5 gf. -52- 200806467 (49) Tg of TMA measurement method Using the thermomechanical measuring device TMA-60 of Shimadzu Corporation, the test piece 2x23mm, at 5gf, according to the method described in "5·17·1 TMA method" of JIS C 6481: 1996 Under the tensile load, the temperature is measured at a temperature of 5 ° C / min. Glass transition temperature Tg measured.

[Table 6] Characteristic Thermoplastic Tripolyimine Resin Extension 1 _ Membrane A-3*1 A-2*1 B-3*1 C-3*1 D-3*1 E-3*1 F- 3*2 A*3 CTE (ppm) MD direction 15 40 21 29 15 45 28 55 TD direction 18 40 23 29 18 45 60 55 Tg (〇C) according to the TMA before extension 250 250 258 250 250 250 250 250 Tg of the extended TMA (°C) 320 320 305 320 320 320 305 — Tg rise according to the extended TMA (°C) 70 70 47 70 70 70 55 — Remarks *1 : Two-axis extension *2 ·•— Axis extension *3 : Unextended embodiment 20 The copper film of the thickness of 18/zm was superposed on one surface of the 1 2.5 // m biaxial thermoplastic polyimide film (A-3) obtained in the stretched film production example 1. (hereinafter also referred to as Cu) foil, a polytetrafluoroethylene resin (hereinafter referred to as PTFE) film having a thickness of 100//m from the double-sided film is sandwiched by a SUS plate, and the SUS plate is doubled. FUJIRON STM, manufactured by FUJICO, which is made of polybenzoxazole as a felt-like cushioning material, -53 - 200806467 (50) is installed in a vacuum high-temperature press machine manufactured by Kitagawa Seiki Co., Ltd., and then Depressurize to 1.0 kPa, with an initial pressure of 10 kgf / cm 2 of pressure After heating to 3 60 °C at a temperature of 5 °C /min, increase the pressure to a secondary forming pressure of 25 kgf / cm2, and keep it for 10 minutes in this state, then slowly cool to room temperature to obtain TPI/Cu. The layer consists of a flexible single-sided copper clad laminate. Example 21 except that the biaxially stretched thermoplastic polyimide film (A-3) of Example 20 was changed to the biaxially stretched thermoplastic polyimide film (B-3) obtained in the film production example 2, The same procedure as in Example 20 was carried out to obtain a flexible single-sided copper-clad laminate having a layer of the desired TPI/Cu layer. Example 22 except that the biaxially stretched thermoplastic polyimide film (A-3) of Example 20 was changed to the biaxially stretched thermoplastic polyimide film (C-3) obtained in Example 3 of the stretched film. The same procedure as in Example 20 was carried out to obtain a flexible single-sided copper-clad laminate having a layer of the desired TPI/Cu layer. The properties evaluated using the flexible single-sided copper-clad laminates obtained in the above Examples 20 to 22 are summarized in Table 7 ° -54- (51) 200806467 [Table 7] Characteristics "Example 20 21 22 Thermoplastic Polyimine resin stretch film A-3 B-3 C-3 Pressurization temperature (.〇360 360 360 cushioning material PBO PBO PBO Adhesive strength (N/mm) TPI film-copper foil warp after warping 〇〇〇Reflow-resistant soldering preparation PPBO··Polybenzoxazole (trade name “FUJIRONSTM”, (share) FUJICO)

The evaluation methods of the adhesive strength, the warpage after the adhesion, and the reflow solderability shown in the above Table 7 are as follows, and the same applies to the examples described later. (The adhesion strength of the flexible copper-clad laminate obtained by the η adhesion strength was measured according to JIS C 648 1 and measured by the following criteria. 〇·· > 0.8 N > mm △ : 0.4 ~0.8 N / mmx : < 0.4 N/mm (2) After the warpage after the adhesion was completed, it was visually judged whether or not the obtained flexible copper-clad laminate was warped, and the judgment criteria were as follows. -55- 200806467 (52) △: There is a little warpage X: There is curling (3) Reflow-resistant solderability ^ The obtained flexible copper-clad laminate is passed through a reflow soldering furnace up to °C, by The swelling was judged visually as follows. _ 〇: no swelling, warping △: slight swelling, warping X: swelling, crimping Example 23 except that the biaxially stretched thermoplastic polythene film of Example 20 was used. In the same manner as in Example 20 except that the (A-3) was changed to the biaxially stretched thermoplastic polyimide resin 2), a flexible single-sided copper-clad laminate having a layer of a target Cu was obtained. Because the coefficient of expansion of the resin is large, warpage occurs after adhesion to the copper foil. (Example 24) A target TPI/Cu flexible single-sided copper-clad laminate was obtained in the same manner as in Example 20 except that the pressurization temperature of Example 20 was changed to 28 °C. As a result, since the pressurization temperature is lower than the softening start temperature of /, the adhesive strength is lower than the degree 260 of the other examples, and the resin film (the line of Α-ΤΡΙ/membrane, and the remaining -3 film form) is judged. -56-200806467 (53) Example 2 5 The flexibility of the layer structure of the desired TPI/Cu was carried out in the same manner as in Example 20 except that the pressurization temperature of Example 20 was changed to 3 90 ° C. The copper laminate was laminated on one side. As a result, the pressure was increased at a temperature exceeding the melting point, so that the resin flowed out and the coefficient of linear expansion increased. Example 26 Except that the cushioning material of Example 20 was not used, Example 20 was used. In the same manner, a flexible single-sided copper-clad laminate having a desired layer of TPI/Cu was obtained. As a result, since no buffer material was used, high surface smoothness could not be obtained. Example 27 In addition to Example 20 The desired stretching layer of TPI/Cu was obtained in the same manner as in Example 20 except that the axially stretched thermoplastic polyimide film (A-3) was changed to the biaxially stretched thermoplastic polyimide film (D-3). Flexible list Copper-clad laminate. Example 2 8 except that the biaxially stretched thermoplastic polyimide film (A-3) of Example 20 was changed to a biaxially stretched thermoplastic polyimide film (E-3), In the same manner as in Example 20, a flexible single-sided copper-clad laminate having a layer of the desired TPI/Cu layer was obtained. Since the linear expansion coefficient of the resin film was large, warpage occurred after adhesion to the copper foil. 200806467 (54) The properties of the flexible single-sided copper-clad laminates obtained in the above Examples 23 to 28 were evaluated and summarized in Table 8. [Table 8] Characteristic Example 23 24 25 26 27 28 Thermoplastic Polyimine Resin stretch film A-2 A-3 A-3 A-3 D-3 E-3 Pressurization temperature (..) 360 280 390 360 360 360 Buffer material PBO PBO PBO ist y\w PBO PBO Adhesion strength (N/ Mm) TPI film-copper foil 〇Δ 翘 warpage after adhesion Δ 〇〇〇〇 Δ reflow resistant g △ 〇〇〇〇 △ remarks | PBO: polybenzoxazole (trade name "FUJIRONSTM", (manufactured by FUJICO) Example 29 A double-sided weight of a 12.5 /zm biaxial thermoplastic polyimide film (A-3) A copper foil having a thickness of 18/m is sandwiched between SUS sheets having a thickness of 100 μm, which is a release film, and a polystyrene oxazole is laminated on both sides of the SUS plate as a felt-like cushioning material. The FUJIRON STM is installed in a vacuum high-temperature press machine manufactured by Kitagawa Seiki Co., Ltd., and then decompressed to 1.0 kPa, and the temperature is raised to 5 ° C / min at a pressure of 10 kg / min at the initial pressure of 10 ° C / min. After C, the pressure was increased to 25 kgf/cm2 of the secondary forming pressure, and kept for 10 minutes in this state, and then slowly cooled to room temperature to obtain a flexible double-sided paste composed of a layer of Cu /TPI/Cu. Copper laminated substrate. -58-200806467 (55) Example 30 except that the biaxially stretched thermoplastic polyimide film (A-3) of Example 29 was changed to a biaxially stretched thermoplastic polyimide film (B-3), The same procedure as in Example 29 was carried out to obtain a flexible double-sided copper-clad laminate having a layer of Cu/.TPI/Cu. Example 3 1 The same procedure as in Example 29 except that the biaxially stretched thermoplastic polyimide film (A-3) of Example 29 was changed to the biaxially stretched thermoplastic polyimide film (C-3). The process proceeds to obtain a flexible double-sided copper-clad laminate composed of a layer of Cu/TPI/Cu. The properties of the flexible single-sided copper-clad laminates obtained in the above Examples 29 to 31 were evaluated and summarized in Table 9. [Table 9] Characteristic Example 29 30 31 Thermoplastic Polyimine Resin Stretch Film A-3 B-3 C-3 Pressurization Temperature (.〇360 360 360 Buffer Material PBO PBO PBO Adhesion Strength (N/mm) TPI Film - warpage of copper foil 〇〇〇 after adhesion, reflow soldering g ctt 1 〇〇〇 Preparation PBO: polybenzoxazole (product * "FUJIR 〇 nSTM", (stock) FUJI CO) Example 3 2 -59- 200806467 (56) 5 0 // m kaptoη ΕΝ (a polyimide film made of Du Pont); this polyimide resin does not have thermoplasticity (thermal reversibility between hardening and softening) Since the linear polymer is not separately extrudable, a commercially available polyimide film (hereinafter also referred to as PI film) is cast by a solution containing a precursor polyamine. a biaxially stretched thermoplastic polyimide film (A-3) having a thickness of 12.5/zm and a copper foil having a thickness of 18/zm on both sides of the roll or on the flat surface after dehydration condensation reaction. The PTFE film having a thickness of 100 μm/m from the double-sided film is SUS plate, and the SUS plate is used. FIHIRON STM, which is a felt-like cushioning material made of polybenzoxazole on both sides, is placed in a vacuum high-temperature press machine manufactured by Beichuan Seiki Co., Ltd., and then decompressed to 1.0 kPa at an initial pressure of 10 kgf/ The pressure of cm2 is raised by 5 ° C / min. After raising the temperature to 360 ° C, the pressure is increased to 25 kgf / cm 2 of the secondary forming pressure, and maintained for 1 〇 minutes in this state, and then slowly cooled to room temperature. A flexible double-sided copper-clad laminate substrate having a layer of Cu / TPI / PI / TPI / Cu was obtained. Example 3 3 In addition to the biaxially stretched thermoplastic polyimide film (A-3) of Example 32 The flexible double-sided copper paste having the layer of Cu/TPI/PI/TPI/Cu for the purpose was obtained in the same manner as in Example 32 except that the film was changed to the biaxially stretched thermoplastic polyimide film (B-3). Laminated plate. Example 3 4 • 60-200806467 (57) In addition to changing the biaxially stretched thermoplastic polyimide film (A-3) of Example 32 to a biaxially stretched thermoplastic polyimide film (C) Except for -3), the same procedure as in Example 32 was carried out to obtain a flexible double-sided sticker of a layer of Cu/TPI/PI/TPI/Cu. Laminates. ^ The properties of the flexible double-sided copper-clad laminates obtained in the above Examples 3 2 to 3 4 were evaluated and summarized in Table 1. [Table 1〇] Characteristic Example 32 33 34 Thermoplastic Polysiloxane Amine resin stretch film A-3 B-3 C-3 Pressurization temperature ΓΟ 360 360 360 Buffer material PBO PBO PBO Adhesive strength (N/mm) TPI film-copper foil 〇〇〇TPI film-PI film 〇〇〇 adhesion翘 翘 〇〇〇 〇〇〇 回流 P P P P PBO: polybenzoxazole (trade name "FUJIRON STM", (stock) FUJICO system) ^ Example 35. Will 1 2 · 5 / m 2 The two-layer flexible polyimide polyimide double-panel having a conductor loop is superposed on both sides of the axial thermoplastic polyimide film (A-3), and the thickness of the film for release film is 100// The PTFE film of the m was smashed with a SUS plate, and the FUJIRON STM, which was a felt-like cushioning material, was placed on both sides of the SUS plate, and was placed in a vacuum high-temperature press machine manufactured by Kitagawa Seiki Co., Ltd., and then depressurized to 1. OkPa, at a pressure of 10kg/min at the initial pressure of 10kg/cm2, the temperature is raised to 36 (after TC, the pressure is increased -61 - 200806467 (58) Force to the secondary forming pressure 25kgf/cm2, hold it for 10 minutes in this state, and then slowly cool to room temperature' to obtain a conductor loop in which the conductor loop is buried in the thermoplastic polyimide film. Multilayer flexible double-sided copper-clad laminate substrate composed of layers of /PI/conductor loop/TPI/conductor loop/PIV conductor loop. Example 3 6 Except that the biaxially stretched thermoplastic polyimide film φ film (A-3) of Example 35 was changed to the biaxially stretched thermoplastic polyimide film (B-3), In the same manner as in Example 3, a multilayer flexible double-sided copper-clad laminate having a desired layer of a conductor loop/PI/conductor loop/TPI/conductor loop/PI/conductor loop was obtained. Example 37 except that the biaxially stretched thermoplastic polyimide film (A-3) of Example 35 was changed to the biaxially stretched thermoplastic polyimide film (c-3), and Example 35 In the same manner, a multilayer flexible double-sided copper-clad laminate composed of a layer of a desired conductor loop/PI/conductor loop/TPI/conductor loop/PI/conductor loop is obtained. The properties of the multilayer flexible double-sided copper-clad laminate obtained in the above Examples 35 to 37 were evaluated and summarized in Table 11. -62- 200806467 (59) [Table 11] Characteristic Example 35 36 37 Thermoplastic Polyimine Resin Stretch Film A-3 B-3 C-3 Pressurization Temperature (.〇360 360 360 Buffer Material PBO PBO PBO Adhesion Strength (N/mm) TPI film, copper foil, TPI film, PI film, warpage after adhesion, reflow solderability, preparation test PBO: polybenzoxazole (trade name "FUJIRONSTM" (manufactured by FUJICO Co., Ltd.) Example 3 8 A two-axis thermoplastic polyimide film having a thickness of 12.5 /zm was superposed on both sides of a two-layer flexible polyimide film double-sided panel in which a conductor loop was formed on both sides ( The copper foil of A-3) and 18//m is smashed with a SUS film having a thickness of 10 〇〇//m from the double-sided film, and the SUS plate is overlapped on both sides. The FUJIRON STM of the felt-like cushioning material is installed in a vacuum high-temperature press machine manufactured by Beichuan Seiki Co., Ltd., and then depressurized to 10 kgf/cm2, and is heated at a temperature of 5 ° C /min at an initial pressure of 1.0 MPa. After 360 °C, increase the pressure to 25kgf/cm2 of the secondary forming pressure, and keep it for 1 〇 minute in this state, then slowly enter After cooling to room temperature, a multilayer flexible double-sided copper-clad laminate in which a conductor loop was embedded in a Cu/TPI/conductor loop/PI7 conductor loop/TPI/Cu layer of a thermoplastic polyimide film was obtained. 9-63-200806467 (60) In addition to changing the biaxially stretched thermoplastic polyimide film (A-3) of Example 38 to the biaxially stretched thermoplastic polyimide film (B-3), In the same manner as in Example 38, a multilayer flexible double-faced copper laminate having a desired Cu/TPI/conductor loop/PI/conductor loop/TPI/Cu layer was obtained. Example 40 Except that Example 3 was The biaxially stretched thermoplastic polyimide film (A-3) of 8 was changed to the biaxially stretched thermoplastic polyimide film (C-3), and the same procedure as in Example 38 was carried out to obtain the intended Cu. Multilayer flexible double-sided copper-clad laminate composed of layers of TPI/conductor loop/PI/conductor loop/TPI/Cu. Evaluation of multilayer flexible double-sided copper-clad laminates obtained in the above Examples 38 to 40 The characteristics are summarized in Table 12.

[Table 12] Characteristic Example 38 39 40 Thermoplastic Polyimine Resin Stretch Film A-3 B-3 C-3 Pressurization Temperature fc) 360 360 360 Buffer PBO PBO PBO Adhesive Strength TH Film - Copper Foil 〇〇〇 (N/mm) TPI film-PI film 翘 翘 〇〇〇 〇〇〇 〇〇〇 〇〇〇 P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P -64 - 200806467 (61) Comparative Example 3 Using a 25 // m unstretched thermoplastic polyimide film (A), a copper foil having a thickness of 18/m was superposed on one surface, and The PTFE film of the thickness of the release film is 〇〇 z z z FU FU FU FU FU FU FU FU FU FU FU FU FU FU FU FU FU FU FU FU FU FU FU FU FU FU FU FU FU FU FU FU FU FU FU FU FU FU FU FU FU FU FU FU a vacuum high-temperature press machine, which is then subjected to a reduced pressure to 1.0 kpa, at a pressure of 10 φ kgf/cm 2 at an initial pressure of 5 ° C /min · a temperature rise to 3 60 ° C, and then the pressure is increased to two times. The molding pressure was 25 kgf/cm2, and was kept in this state for 10 minutes, and then slowly cooled to room temperature to obtain an unstretched TPI/Cu. Layer constituting one surface of the flexible copper-clad laminated board. In the obtained flexible single-sided copper-clad laminate substrate, since the unstretched thermoplastic polyimide film used has a large coefficient of linear expansion, significant warpage (crimping) occurs after adhesion of the copper foil. . Comparative Example 4 The same procedure as in Example 20 was carried out, except that the biaxially stretched thermoplastic polyimide film (A-3) of Example 20 was changed to the one-axis stretch thermoplastic polyimide film (F-3). A flexible single-sided copper-clad laminate composed of a layer of one-axis extended TPI/Cu is obtained. In the obtained flexible single-sided copper-clad laminate substrate, the linear expansion coefficient in the MD direction (longitudinal direction of the film) of the thermoplastic polyimide film (E-3) used is close to that of the copper foil. Oh, it causes significant warpage (crimping) after adhesion to the copper foil. -65- (62) 200806467 Comparative Example 5 A flexible single-sided copper layer having a layer structure of tpi/Cu was produced in the same manner as in Example 20 except that the pressurization temperature of Example 20 was changed to 240 °C. Plywood. As a result, since the Tg of the thermoplastic polyimide film having a lower Tg is less than the Tg, the biaxially stretched thermoplastic polyimide film does not start to soften, so that it cannot adhere. The properties of the flexible single-sided copper-clad laminates obtained in the above Comparative Examples 3 to 5 were evaluated and summarized in Table 13. [Table 13] Characteristic Comparative Example 3 4 5 Thermoplastic Polyimine Resin Stretch Film A F-3 A-3 _ Pressurization Temperature (.〇360 360 240 A Buffer Material PBO PBO PBO _ Adhesive Strength (N/mm) TPI Film-copper foil 〇〇X After warping XX a reflow-resistant solderability — — After warping, the warpage is noticeably warped significantly. The test is not sticky. PBO: Polybenzoxazole (trade name “FUJIRONSTM”, [Production of FUJICO] [Industrial Applicability] Since the flexible laminate of the present invention has a thermoplastic polyimide film as an adhesive layer, it can be used for a cover film of various flexible substrates or planar heat-generating bodies. And various technical fields such as a laminate of a metal foil such as stainless steel, aluminum, or nickel, and the like, particularly suitable for use in a flexible printed circuit board - 66-200806467 (63), or a flexible printed circuit The manufacture of a recording automatic bonding (TAB) product of a board. [Simple description of the drawing] [Fig. 1] shows the TMA curve of a thermoplastic polyimide film unstretched film and a biaxially stretched thermoplastic polyimide film. Pattern diagram. 2] is a schematic partial cross-sectional view showing an example of the φ structure of the flexible double-sided copper-clad laminate according to the present invention. [Fig. 3] shows the structure of the flexible double-sided copper-clad laminate according to the present invention. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 4] is a schematic partial cross-sectional view showing an example of the structure of a multilayer flexible laminate according to the present invention. [Fig. 5] shows a multilayer in accordance with the present invention. A schematic partial cross-sectional view of another example of the structure of the flexible laminate. φ [Explanation of main component symbols] ^ 1 : Thermoplastic polyimide film (or biaxially stretched thermoplastic polyimide film) 2 : Copper foil 3: Polyimine resin film 4: conductor loop layer -67,

Claims (1)

200806467 (1) X. Patent Application No. 1 · A flexible laminate comprising a metal foil layer/thermoplastic polymer layer formed by adhering a metal foil layer or a conductor loop layer on at least one side of a thermoplastic polyimide layer An imide layer or/and a conductor loop layer/thermoplastic polyimide layer; a flexible laminate; characterized by the above thermoplastic polyimide layer being obtained by melt-extruding a thermoplastic polyimide film resin A thermoplastic polyimide film or sheet of thermoplastic polyimide, or a film formed from a biaxially stretched thermoplastic polyimide film φ film or sheet. 2. The flexible laminate of claim 1, wherein the thermoplastic polyimide resin has a glass transition temperature (Tg) of from 180 to 280 °C. 3. The flexible laminate according to claim 1, wherein the thermoplastic polyimide resin is cut at a temperature of 30 ° C higher than the melting point of the resin by a range of 50 to 50 ° sec T1] The melt viscosity measured by the speed is 5 x lO1 ~ lxl04 [Pa · S] ° 4. The flexible laminate according to claim 1, wherein the two-axis φ extended thermoplastic polyimide film or sheet A thermoplastic polyimide film or sheet obtained by melt-extruding a thermoplastic polyimide, and a biaxially stretched thermoplastic polyimide film obtained by biaxial stretching. 5. The flexible laminate according to claim 1, wherein the biaxially stretched thermoplastic polyimide film or sheet has any of MD direction (long film direction) and TD direction (film width direction) The thermal expansion α2〇-2〇〇 is in the range of 5xl〇-6~30χ10·6/Κ. 6. The flexible laminate according to claim 1, wherein the two-axis-68-(2) 200806467 extended thermoplastic polyimide film or sheet, MD direction (film longitudinal direction) and TD direction (film The difference in thermal expansion ratio α 2Q_2 in the width direction is 20χ1 (Γ6/Κ. 7) The flexible laminate according to claim 1, wherein the biaxially stretched thermoplastic polyimide film or sheet, The glass transition temperature Tg measured by thermomechanical analysis (ΤΜΑ) according to the method described in "5.17.1ΤΜΑ method" of JIS C 648 1 : 996, compared with the glass transition of the thermoplastic polyimide film or sheet before stretching The temperature Tg is 10 to 80 ° C. 8. The flexible laminate according to claim 1, wherein the thermoplastic polyimide resin is a crystalline thermoplastic polyimide resin. The flexible laminate of the present invention is a thermoplastic polyimide resin which is composed of a mixture of a crystalline thermoplastic polyimide resin and another thermoplastic resin having a melting point of 2800 to 350 ° C. 1 〇· For example, the scope of patent application is 1 The flexible laminate of any one of the items 9, wherein the thermoplastic polyimide resin is a thermoplastic polyimide resin having a repeating structural unit of the following formula (i), o=c\\>HO (1 ) (where X is a direct bond, -S〇2-, -CO-, -C(CH3)2-, -C(CF3)2- or -S- , R1, R2, R3, and R4 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group, a halogenated alkyl group, a halogenated alkoxy group, or a halogen-69-(2) 200806467 (3) atom Further, Y is a group selected from the group consisting of the following formula (2)) The flexible laminate according to any one of claims 1 to 9, wherein the thermoplastic polyimide resin is a thermoplastic polyimide resin having a repeating structural unit of the following formula (5) , The flexible laminate according to any one of claims 1 to 9, wherein the thermoplastic polyimide resin is a thermoplastic having a repeating structural unit of the following formula (6) and formula (7) Polyimine resin, -70- (6) (7) (4) 200806467 t (where m and n represent the molar ratio of each structural unit, m/n = 4 to 9 range). The flexible laminate according to any one of claims 1 to 9, wherein the thermoplastic polyimide resin is a repeating structural unit having the following formula (6) and formula (8); The thermoplastic polyimine resin, and the molar ratio of the repeating structural unit represented by the following formula (6) to the repeating structural unit represented by the following formula (8) is in the range of 1:0 to 0.75: 0.25. (6) i? N (8) 1 4 . A method for producing a flexible laminate comprising a metal layer or a conductor loop layer bonded to at least one side of a thermoplastic-71 - 200806467 (5) polyimide layer A method for producing a flexible laminate of a foil layer/thermoplastic polyimide layer or/and a conductor loop layer/thermoplastic polyimide layer; characterized by thermoplasticity obtained by melt-extruding a thermoplastic polyimide film Polyimide resin, film or sheet, or a film or a sheet of a biaxially stretched thermoplastic polyimide film, which is adhered to a metal foil or a conductive circuit layer by heating and pressing. 1 5 - A method for producing a flexible laminate, characterized in that a thermoplastic polyimide film is melt-extruded on a treated side of a copper foil having at least one φ surface subjected to rough surface treatment or adhesion treatment The obtained thermoplastic polyimide film or sheet, or the biaxially stretched thermoplastic polyimide film or sheet, and the opposite side of the film, overlap at least one of which is roughened or adhesively treated The treated side of the copper foil is then heated and pressurized. 1 6 — A method for producing a flexible laminate, characterized in that a thermoplastic polyimide film is melt-extruded on both sides of a polyimide film having no treatment or double-sided adhesion treatment. a thermoplastic φ polyimine resin film or sheet obtained by press forming, or a biaxially stretched thermoplastic polyimide film or sheet, and at least one side of which is subjected to rough surface treatment or X-adhesive treatment The treated side of the copper foil overlaps inwardly and then is heated and pressurized. 17. A method of producing a flexible laminate, characterized in that a double-sided flexible substrate which is formed into a circuit, which is not treated or double-sidedly adhered, is in contact with each other to form a thermoplastic polyimide resin. The thermoplastic polyimide film, film or sheet obtained after melt extrusion molding, or a film or sheet of a biaxially stretched thermoplastic polyimide film is then heated and pressurized. 1 8 - A method for producing a flexible laminate, characterized in that it is formed on the outer side of a double-sided flexible substrate which is formed into a -72-200806467 (6) circuit, without treatment or double-sided adhesion treatment Overlaying a thermoplastic polyimide film or sheet obtained by melt-extruding a thermoplastic polyimide film, or a biaxially stretched thermoplastic polyimide film or sheet, and then at least one side is roughened or The treated side of the adhesively treated copper foil is overlapped in the inner side, and then heated and pressurized. The method for producing a flexible layer φ ply according to any one of claims 14 to 18, which is a film or sheet of a thermoplastic polyimide film or a biaxially stretched thermoplastic polyimide film or sheet For those who apply surface modification treatment on one or both sides. The method for producing a flexible laminate according to any one of claims 14 to 18, wherein the heating and pressurization is carried out at a temperature higher than a glass transition temperature Tg of the thermoplastic polyimide resin to be used. . The method for producing a flexible laminate according to any one of claims 1 to 4, wherein the heating and pressurization is performed by a thermoplastic polyimide film or a sheet or a biaxially stretched thermoplastic. The polyimide film of the polyimide film or the film has a glass transition temperature Tg or higher and a temperature equal to or lower than the melting point. The method for producing a flexible laminate according to any one of claims 1 to 4, wherein the heating and pressing are carried out at a temperature of 300 to 380 °C. The method for producing a flexible laminate according to any one of the above claims, wherein the heating and pressurization is performed at a pressure connected to the heated and pressed material. A felt-like cushioning material is interposed between the plate and the pressure plate of the press machine. The method for producing a flexible laminate according to claim 23, wherein the felt cushioning material is an aromatic polyamine or a polybenzoxazole. -74-